EA037155B1 - Method for processing ores, low-quality concentrates and technogenic copper waste - Google Patents

Abstract

The invention relates to the field of metallurgy industry and can be used for production of commercial copper concentrates from various copper-containing raw materials, and for extraction of precious metals, for example, when processing gold-arsenic concentrates. The technical result is an increase in extraction degree of target components to a high grade sulfide concentrate free of dead rock, suitable for slag-free melting to produce blister copper. This is achieved by provision of a method for processing ores, low-quality concentrates and technogenic copper waste, comprising the steps of crushing, degradation, beneficiation, densification, filtration and leaching in the presence of oxidizers and complexing agents when heating the pulp, wherein, according to the invention, used as a source of oxidizers are natural raw materials or technogenic waste containing iron(III), manganese(IV), off-grade concentrates of iron(III), manganese(IV), or ferromanganese(IV) ore, and off-grade concentrates or sludge of alumina industry, which are further subjected to acid leaching; then the obtained solution is used for leaching the non-ferrous raw metals, in particular, copper; after cake blow, the filtrate is processed using well-known metallurgy practices.

Description

(54) METHOD FOR PROCESSING ORE, LOW-GRADE CONCENTRATES AND INDUSTRIAL WASTE OF COPPER (43) 2020.11.30 (96) KZ2019 / 036 (KZ) 2019.05.17 (71) (73) Applicant and patent owner:

ZHUMASHEV KAL KAMAN; NAREMBEKOVA AITBALA;

KATRENOV BAUYRZHAN BORANBAEVICH (KZ) (72) Inventor:

Zhumashev Kalkaman, Narembekova Aitbala, Katrenov Bauyrzhan Boranbaevich, Zharmenov Abdurasul Aldashevich, Terlikbaeva Alma Zholdasovna (KZ) (74) Representative:

Tusupova M.K. (KZ) (56) RU-C1-2133293 SU-A1-1280902

EA-B1-9503 WO-A1-2010126593

037155 B1

037155 Bl (57) The invention relates to the field of metal metallurgy and can be used in the production of commercial copper concentrates from various types of copper-containing raw materials, as well as for the opening of precious metals, for example, in the processing of gold-arsenic concentrates. The technical result is to increase the degree of extraction of target components into a rich sulphide concentrate without waste rock, suitable for slag-free smelting for blister copper. This is achieved by the fact that the method of processing ores, low-grade concentrates and man-made copper wastes, including the stages of crushing, grinding, enrichment, thickening, filtration and leaching in the presence of oxidants and complexing agents when heating the pulp, according to the invention, natural raw materials or man-made wastes are used as a source of oxidants containing iron (III), manganese (1U) - substandard concentrates of iron (III), manganese (1U) or ferromanganese (IV) ores and substandard concentrates or slimes of alumina production, then they are subjected to acid leaching, then the resulting solution is used for leaching raw materials non-ferrous metals, in particular copper, the filtrate after separation of the cake is processed by known methods in metallurgy.

The invention relates to the field of metallurgy of metals, in particular to combined methods of enrichment of metallurgical raw materials and man-made waste, and can be used when obtaining commercial copper concentrates from various types of copper-containing raw materials (rough concentrates from flotation concentration of stale tailings or off-balance ores, slags), and for opening precious metals, for example, when processing gold-arsenic concentrates.

In non-ferrous metallurgy, various types of natural raw materials are involved in production, mainly sulfide, oxidized and mixed ores. Sulfide minerals of copper (chalcopyrite, bornite, chalcocite, covellite) are most difficult to open, therefore, an effective method of opening for them is applicable for opening sulfide minerals of other non-ferrous metals (lead, zinc) and minerals of iron group metals (arsenopyrite, pyrite, chalcopyrite, etc.) .).

Copper from oxidized ores (more than 70% oxidized minerals) is recovered by various leaching methods using acidic or ammonia solutions. The most common method for processing refractory oxidized copper ores, which consists in leaching oxidized copper minerals with acid, cementation of copper from a solution with iron powder, flotation of cement copper from an acidic solution to obtain a copper concentrate. The method is applied for the processing of refractory oxidized ores of the Kalmakirsky deposit at the Almalyk mining and metallurgical plant / Mitrofanov S.I. and others. Combined processes of processing of non-ferrous metal ores, M., Nedra, 1984, p. 50 /.

The disadvantages of this method are:

the high cost of implementation due to the use of an iron scrub, which reacts with acid, while the consumption of both sulfuric acid and iron scrub increases; low copper recovery by cementation with iron scrub and flotation of cement particles;

incompatibility of recovery of oxidized and sulphide copper minerals into flotation concentrate and loss of sulphide copper or the complexity and high cost of combining flotation recovery of sulphide copper minerals, as is often suggested for processing mixed ores. If in the first case there is a loss of sulfide copper in the tailings and copper is extracted from the solution by complex methods, then in the second case, a poor flotation concentrate is obtained, due to the presence of the so-called waste rock of silicon dioxide and iron compounds.

As an example of processing mixed ores, one can take the Method of complex processing of lean off-balance ores, where sulfide minerals from the mixed ore of the Taskora deposit (Kazakhstan) are extracted into a flotation concentrate, and oxidized copper minerals are extracted from the tailings, by leaching at 80 ° C and L: T = 5 : 1 solution of sulfuric acid 80 g / l. End-to-end copper recovery 89.15% / KZ 25311 A4, publ. 12/14/2012 /.

A common problem and disadvantages of all known methods of ore beneficiation, including combined chemical methods, is reduced to obtaining a commercial concentrate from poor sulphide ores, especially the possibility of obtaining a high-value concentrate without waste rock from any ores, man-made waste with an increase in the degree of copper recovery, which remains an unsolved problem. worldwide.

The main directions are associated with an attempt to transfer copper into a solution for further extraction by known methods or to reduce the content of silicon dioxide and iron.

The most difficult hydrometallurgical methods are used to open up copper sulfide minerals; therefore, the flotation method is the main method for enriching sulfide ores. During pyrometallurgical processing of sulfide copper concentrates with purification from iron and silicon impurities (basic method), including the stages of melting into matte and converting the matte, dump slag is formed - waste with which copper and iron are lost, and also environmental problems arise, in addition, processing by these methods non-commercial or low-grade concentrates are not profitable / M.A. Fishman. Fundamentals of beneficiation of non-ferrous metal ores. Ed. Bosom. M.1968. with. 164-165 /.

Therefore, the proposed method relates to the production of high-grade copper concentrates without waste rock by hydrometallurgical methods from all types of copper raw materials - oxidized, mixed and sulfide ores.

To refine low-grade sulfide concentrates to marketable, various methods are proposed that can be considered as analogs and prototypes to the proposed one. The processes of purification from iron and silicon by hydrometallurgical methods require the use of various reagents, therefore, separate processes.

Known autoclave sulfuric acid leaching methods at high temperatures (above 180 ° C) and under oxygen pressure, which allows you to partially extract copper and iron into the solution / S.S. Naboychenko, L.P. Nee, Ya.M. Shneerson, L.V. Chugaev. Autoclave hydrometallurgy of non-ferrous metals // 1995. Yekaterinburg. 282s /.

Disadvantage: incomplete extraction of copper (below 90%), expensive and complicated method.

Various options for leaching a concentrate containing copper minerals - chalcopyrite, covellite and bornite with sulfuric acid with concentrations of 50-300 g / l at S: W = 1: 4 and 25-75 ° C for 1-6 hours, as with oxygen supply into the reactor and without it in operation Exploratory studies on sulfuric acid leaching of sulphide copper concentrate from the Erdenet deposit (Mongolia)

- 1 037155 / ISBN 5-7262-0710-6. Scientific session MEPhI-2007. Volume 9 // Physical chemistry of solutions. A. Hammash,

A.S. Medvedev).

The maximum extraction of copper into the solution did not exceed 40%, which is associated with the course of the reactions:

Cu ₉ Fe ₉ Si ₆ + Cu ₅ FeS ₄ + FeS ₂ + O ₂ + 2H ₂ SO ₄ = 10CuFeS ₂ + 4CuS + 2FeSO ₄ + 2H ₂ O

The main disadvantages of these works include the low degree of copper extraction, due to the ineffectiveness of the regeneration of ferric iron by atmospheric oxygen from the sulfide iron minerals contained in the concentrate.

The effect of ferric iron obtained by bacterial and chemical oxidation of ferrous iron under conditions of leaching of sulfide copper concentrate at ambient temperature with acid solutions and at elevated temperatures of 85-95 ° C / 1 has been studied. Development of a method for leaching sulfide concentrates with sulfuric acid solution and ferric iron obtained by immobilized mass // Abstract of the thesis. Cand. dissertation, Gusakov M.C.niscu.ru/work/989417/ Razrabotka /.

The main disadvantages of the prototype include:

the relative high cost of regeneration of oxidants in comparison with the proposed method.

the duration or the need to create special conditions for the regeneration of oxidants, which limits the rate of the leaching of copper (non-ferrous metals).

The closest in technical essence to the proposed invention is a method for processing ores, low-grade concentrates and industrial waste of copper, including the stages of crushing, grinding, enrichment, thickening, filtration and leaching in the presence of oxidants and complexing agents when heating the pulp, in which the addition of ammonium sulfate at the stage grinding ore for transferring oxidized copper into solution and extraction by known methods from solution / KZ 29755 A4, publ. 04/15/2015 /.

The disadvantages of the analog include:

low copper recovery (78%), high consumption of expensive reagent - ammonium sulfate and cementation of copper on balls during grinding.

The objective of the invention is to develop a cheaper and simplified method for processing ores, low-grade concentrates and man-made copper waste with improved technical characteristics.

The technical result is to increase the degree of extraction of target components into a rich sulphide concentrate without waste rock, suitable for slag-free smelting into blister copper, bypassing the stage of smelting for matte with associated extraction of iron into commercial concentrate.

This is achieved by the fact that the method for processing ores, low-grade concentrates and industrial waste of copper, including the stages of crushing, grinding, enrichment, thickening, filtration and leaching in the presence of oxidants and complexing agents when heating the pulp, according to the invention:

as a source of oxidants, natural raw materials or industrial waste containing iron (III), manganese (IV) are used - substandard concentrates of iron (III), manganese (IV) or ferromanganese (IV) ores and substandard concentrates or sludge of alumina production, then they are subjected to acid leaching, then the resulting solution is used to leach raw materials of non-ferrous metals, in particular copper, then lead is precipitated from the technological solution of non-ferrous metals by the addition of soluble sulfates of accompanying metals in solution - iron, copper, zinc, then after separation of lead sulfate from the filtrate - copper sulfides and its companions - silver, rhenium, then the main part (80-90%) of the filtrate is sent into circulation for leaching, the other part of the filtrate (20-10%) is taken out for complete processing by neutralization with calcium or barium hydroxides for fractional precipitation of zinc and iron, then carry out the regeneration of hydrochloric acid by adding an equivalent amount of sulfuric acid to chlorine ion.

The claimed invention is distinguished by the use of cheap and affordable natural raw materials - substandard iron or ferromanganese ores, industrial waste - alumina production sludge after autoclave extraction (Bayer process), etc., as a source of ferric or manganese oxidizer (III or IV) and from them, the target metals are transferred into solution by leaching with circulating solutions of mineral acids, in particular hydrochloric acid containing ammonium chloride, under known temperature conditions of 85-95 ° C:

Fe ₂ O ₃ + ZNS1 = FeCl ₃ (1).

The hot clarified solution of oxidizing agents is fed through the settler to the reactor for leaching ore concentrates or man-made copper waste (in principle, it is applicable for any non-ferrous metals) under known temperature conditions of 85-95 ° C

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Fe ₅ CuS ₄ + 12FeCl ₃ = 17FeCl ₂ + CuCl ₂ + 2S ₂ (2)

FeAsS + 2FeCl ₃ = 3FeCl ₂ + 0.5S ₂ (3)

MeS + 2FeCl ₃ = 2FeCl ₂ + MeCl ₂ + 0.5 S ₂ (4) (where Me is Cu, Pb, Zn, Fe, Ni, Ag, Au (they pass into solution in the form of chloride ammonia complexes).

If there is a significant amount of lead in the solution, it is first precipitated in the form of poorly soluble sulfate and the filtrate II is sent to the precipitation of copper and satellites.

From the concentrated concomitant impurities (Ca, Ba, Zn, Fe) filtrate II, hydrogen sulfide precipitates heavy non-ferrous metals (Cu, Pb, Ag, Au), the precipitate is separated by filtration and the main part (90-80%) of the filtrate is recycled.

Part of the filtrate is withdrawn for complete processing by neutralization with calcium or barium hydroxides at pH 8-9, a mixture of hydroxides (zinc and iron) or after fractional precipitation is separated and from filtrate III, hydrochloric acid is regenerated with sulfuric acid;

The filtrate is fed to the head of the process.

An essential distinguishing feature (novelty) is the transfer of ferric iron from substandard ferrous raw materials and waste to a solution by leaching with solutions of acids, in particular hydrochloric acid, and the use of the resulting solution as cheap oxidizing agents for opening refractory copper minerals during leaching of the corresponding metallurgical raw materials with subsequent production from technological solution of commercial concentrates of non-ferrous metals, in particular copper and commercial iron concentrate.

The invention works as follows.

Examples. Experiments on obtaining a solution of oxidizing agents.

To obtain oxidants, ferromanganese ore from the Tur deposit (Kazakhstan) was taken,%: Leaching was carried out with a hydrochloric acid solution containing 10-17.5% HCl (1: 1) at W: T = 45: 1 and a temperature of 70-95 ° C, sample in all experiments represented 25 g and the number of revolutions of the paddle mixer 250 rpm.

Experimental conditions and results are shown in table. one.

Table 1. Results of experiments on obtaining solutions of oxidizing agents from ore samples from the deposit

Round: 15.62 Fe (III); 15.03 Mn (IV); 39.01 SiO ₂ ; 1.88 CaO

No. nn t, ° C τ, hour [НС1] W: T Trick Extracted into solution,% r % % Σ Fe + Mn one 84 one 15 4: 1 17.01 68.04 31.96 59.0 2 94 one ten 4: 1 21.5 86.00 14 25.87 3 70 2 15 4: 1 18.14 72.56 27.44 50.70 four 70 one 15 4: 1 18.81 75.24 24.76 45.75 five 70 one 15 5: 1 18.45 73.80 26.2 48.41 6 70 one 1: 1 4: 1 16.53 66.12 33.88 62.60 7 70 one 1: 1 5: 1 16.16 64.64 35.36 65.33 8 70 2 1: 1 5: 1 14.99 59.96 40.04 73.98 nine 90 2 1: 1 4: 1 11.74 46.96 53.04 98,00 ten 90 one 1: 1 5: 1 13.58 54.32 45.68 84.40 eleven 90 2 15 5: 1 14.65 58.60 41.4 76.49 12 18 2 1: 1 5: 1 23.23 93.00 7.0 12.3

Leaching of iron and manganese with acid solutions is known and, as can be seen, from the data in the table, the maximum total extraction is achieved at 90 ° C, within 2 hours. maximum cumulative recovery).

Experience 13 (solution production).

As a source of iron (III) washed dry red sludge of the Bayer branch of AO Aluminiy Ka-3 037155 zakhstan composition,%: SiO2 - 3.13; Fe2O ₃ - 48.36; Al2O ₃ - 42.21; Na2O 1.44; CaO - 2.55. Leaching was carried out in all cases under the condition of experiment 9 and the combined accumulated solution with an iron (III) content of 72.2 g / l was used to leach copper raw materials.

Experiments on the chemical enrichment of copper raw materials.

In all experiments 14-18, an acidic solution with an iron (III) concentration of 72.2 g / l was used for leaching, at a temperature of 95 ° C for 60 minutes and at a solution consumption of L: T = 5: 1, with a sufficient amount of iron solution ( Ш) to a sample of concentrate according to the reaction equation:

FeCh + MeS (FeS + CuS + PbS) = MeCl ₂ + FeCl ₂ + 0.5S ₂ , while the excess acid served to neutralize metal carbonates and create an acidic environment to prevent hydrolysis of iron (III).

Dried concentrate products were analyzed.

Experience 14.

Rough concentrate (main flotation) of the Satpayevsky concentrating plant (SOF), in which copper minerals are mainly (80%) presented in the form of chalcocite - Cu ₂ S. The concentrate is low in sulfur and low in iron.

The consumption of iron (III) in the solution for 100 g of the concentrate of the Satpayevskaya RP will be 0.148 l or Zh: T = 1.5: 1 (by calculation):

The required W: S can be selected by changing the concentration of Fe (III) in the solution used for leaching. To ensure the extraction of silver, a chloride complexing agent, ammonium chloride, in an amount of 10 g (25%), was added to the solution, and L: T was brought to 2: 1 with water.

The conditions and results for the purification of sample 1 from iron and silicon dioxide with a solution of an oxidizing agent developed under the conditions of experiment 9 (Table 1) are given in table. 2.

Experience 15.

Table 2. The composition of the initial sample of the substandard concentrate of the Satpayevsky-No.1 concentrate, weighed in all experiments for 20 years (experiment 14)

Concentrate composition, % Cake (yield 79.9%) after leaching at a temperature of 95 ° C for about minutes and W: T = 2: 1 Content in cake,% Izvl. in solution,% Through extraction to concentrate Note % r Si 5.38 0.05 99.2 99.2 5,337 Fe 4.11 0.37 92.8 - Fe in solution Ag (g / t) 87.8 5.1 95.4 95.4 95.4g / t S 3.94 4.72 - - 2.48 Due to H ₂ S Mp 0.129 - - - - Not analyzed Zn 0.04 Not obn. 99.9 99.9 - Zn in solution Al 8.35 9.00 14.1 - - A1 in solution Mg 0.56 - - 0 - Mg in solution Pb 0.15 0.008 95 95 0.14 SiO ₂ 59.8 74.84 - 0 SiO ₂ in the cake differently. CO ₂ 9.30 - - 0 Into gases CaO 6.05 0.01 99.9 0 In solution Marketable concentrate yield: - 7.96

As you can see from the table. 2, when a sufficient amount of iron (III) is used in relation to metals subjected to chlorination, a high recovery of copper and other non-ferrous metals is achieved. The addition of complexing agents (NH4Q or NaCl) for the extraction of poorly soluble chlorides of noble metals, copper is well known and in our case it is necessary for the extraction of silver, which, in the presence of ferrous iron, cannot transform into a soluble form.

The solution can be processed by any known methods, for example, by the action of alkaline reagents, in particular, zinc, aluminum, iron are precipitated with milk of lime, and then by adding sulfuric acid, hydrochloric acid is regenerated.

Experience 16.

Test with oxidized ore (carbonate) quarry KrestoCentr with a copper content of 1.04%, of which 75% is oxidized. Fe (III) consumption / 100 g of ore:

Leaching was carried out at 95 ° C for an hour with a solution of iron (III) 2.75 g / l, containing sulfuric acid 65 g / l at W: T = 2: 1 (total acid consumption per 1 ton of ore 0.13 t) for 1 h. The copper content in the dried cake is 0.04%.

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Experience 17.

Test with rough concentrate obtained from ZhOF tailings.

Rough concentrate was obtained from ZhOF tailings by repeated flotation under known conditions (yield

8.4%) with composition,%: 1.43 copper; 1.8 g / t silver; 0.2 g / t rhenium; 16.7 iron; 11.9 calcium, which was subjected to chemical enrichment under the same conditions. The results are shown in table. 3.

Table 3. The main chemical composition of the stale tailings of the ZHOF (Zhezkazgan Concentrating Plant) No. 1,2 of the tailing dump No. 1

ZHOF tails Extraction to rough concentrate End-to-end extraction into salable concentrate Content in commercial concentrate Component % % r % r % (g / t) Si 0.15 80 0.12 80 0.12 fifty Ag, g / t 2.56 65 1.66 65 1.66 435g / t Fe 1.98 70 1.39 70 - - Re, g / t 0.39 fifty 1,2 fifty 1,2 71.4g / t Si 30.0 - Ca 3/0 - Zn 0.11 75 0.08 75 - - Pb 0.09 70 0.06 70 0.06 25 Cd, g / t 3.0 - S 0.35 0.25 0.06 25 Al 6.2 - Marketable concentrate yield 0.24 0.24%

The output of the marketable concentrate is 0.24%. Zinc and iron remain in solution, from where they are extracted by known methods (for example, there will be experiment 17).

Experience 18.

Waste slags of the Zhezkazgan Copper Smelting Plant (ZMZ).

Table 4. Initial slag and processed products

Initial slag Recovery from 100 g of slag into concentrate Component YOU Structure Si PL Zn Fe % (g / t) % r % r % r % r Copper 0.65 99.1 0.644 - - - - - - Lead 0.48 - - 97.3 0.467 - - - - Zinc 0.69 - - - - 98.6 0.68 - - Iron 15.82 - - - - - 92.6 14.65 Gold, g / t 0.11 75 0.0825 - - - - - - Silver, g / t 8.44 98.1 8.28 - - - - - - Total sulfur 0.51 - 0.42 - - - - - - SiO ₂ 49.2 0 - - - - - - CaO H, 7 0 0 0 0 0 0 0 0 Concentrate yield 1.36 1.06 0.75 0.75 - 0.87 - 20.2 Me content 47.35 60.75 62.3 78.16 - 72.5 -

As can be seen from the data in the table. 4 there is a significant amount of copper, lead, zinc and iron in the slag, therefore it is desirable to extract them into separate products (concentrates). To do this, after extraction, iron sulfate was added to the solution (other soluble sulfates - zinc or copper) and after separation by filtration of the precipitated precipitate of lead sulfate, copper, silver and rhenium were precipitated from the filtrate with hydrogen sulfide into copper monoconcentrate.

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Iron was precipitated from the new filtrate with zinc hydroxide, then zinc was precipitated with milk of lime into separate concentrates.

So, the advantage of the proposed method of enrichment of sulfide ores from the known is to obtain sulfide concentrate without waste rock, suitable for slag-free smelting for blister copper, bypassing the stage of smelting on matte with associated extraction of iron into commercial concentrate.

Claims (1)

1. A method for processing ores, low-grade concentrates and man-made copper wastes, including the stages of crushing, grinding, enrichment, thickening, filtration and leaching in the presence of oxidants and complexing agents when heating the pulp, characterized in that natural raw materials or man-made wastes are used as a source of oxidants, containing iron (III), manganese (IV) - substandard concentrates of iron (III), manganese (IV) or ferromanganese (IV) ores or substandard concentrates or slimes of alumina production, then they are subjected to acid leaching with hydrochloric acid, then the resulting solution is used for leaching raw materials of non-ferrous metals, then from the technological solution of non-ferrous metals, lead is first precipitated by the addition of soluble sulfates of accompanying metals in solution, selected from iron, copper, zinc, then after separation of lead sulfate from the filtrate, sulfides of copper and its companions - silver, rhenium, are precipitated, then the main part (80-90%) filter Ata is sent into circulation for leaching, the other part of the filtrate (20-10%) is taken out for complete processing by neutralization with calcium or barium hydroxides for separate precipitation of zinc and iron, then hydrochloric acid is regenerated by adding an equivalent amount of sulfuric acid to chlorine ion. Evra Eurasian Patent Organization, EAPO